Spray composition



- PatentedJune 25, 11940 actas armutv comosrTroN Gerald Hi. Coleman and Clarence Lilloyle.' Mid- Md,fMich,`,{assignors to The `Dow Chemical .Y

Company, `Midla nd, Mich., a corporation of Nallrwinr. Application August 17, 193s, Aseran No. 225,416`

l n f` f iz claims. (ci. ier-'24) f This invention' concern?. Ciiivlwsitions particularly ac lapftedV f ork combating iiies,1 mosquitoes, moths, and similar insects.

`Petroleum distillate sprays containing extracts 5 of suchl insecticidal piant'products aspyrethrum owers'i derris, cube, barbasco, and the like, are widely used forthe control of `household insect pests'. Pyrethrinfcontaining sprays havelaquick paralyzing action on nies, but generallyfspeaking 10 the kill obtained therebyis low compared to the percent knockdown.j 'otenoneconiining compositions givea ,more permanent control, but are relatively-slovsr intheir actioni'requiring aconsid'- l`erable`1xiriod of time to :kill insect pests contacted l5 therewith. Both of -theabove-mentioned toxicants also suffer lfrom thev4 disadvantage that 4they are unstableto kheat and lightand upon storage lose their-.electivene'ss to afconsiderabledegree.

- Weghavediscoveredrthat when 'a small .amount 20 of an*,aryloxyfhalo-dialkyl-ether is-.-added to 'solutions oi insecticidal` plant-.products containing Such. toxicants 'asmy'rethrin :andrei-renoue... improved spray compositions arelobtained `which are more stable to heat and ,light andhavea g5 v greaterparalyzing KV effectand greater lethaleifect on ifrifsfectsl3th n. riginal extract-:containing @mismos-s.; 'rrhe'se Sprays siveagkill ,on .meis 'and V"I "ielated 'insee which more "closely "approxif mates "the" i percentage" knockdown of such' lpests lo than fdo common V'household insecticide sprays heretofore employed. Furthermorathe aryloxyhalo-dialkyl ethers are Aeiiicient.substitutes'ior thel extracts of-f-insecticidalf plant products in` spray compositions,solutionsgof such synthetic ether compounds y.comparing favorably .inlrtoxic eiect with the plant Vextracts and having the -added advantage of being substantially colorless l and odorless,- and being completely stable 'to heat,-

light, and air.

o when the aryloxy-ham-dialkyl etherfis 'used alone as the toxicant i`n` an insect spray `compo-L- sition, a concentration from about 2 yto about1. 1 0"^" -per cent in an-'Iinert organic solvent is satisfacfv tory. For use in stabilizing and/or fortifying'the common r sprayompositions YconriprisirlgDfi- Vrethrin or msnen@- theA arrlOXr-halO-@ialkyl 'tm-lint f fmifmt 0:5

f amples,l afc'ontrol pyrethrin solution was eming spray compositions are those having the following formula s wherein each R vrepresents an alkyl residue containing'not more than 3 carbon atoms, each X represents 'halogen'. Y vrepresents hydrogen or an alkyl group;v containing not more than 6 carbon atoms, n' is van integer not greater than 5, and m -an'integer notgreater than 2. The above compounds may be prepared by reacting a halophenol or 'allwl-halo-phenol with dihalo-dialkyl Iether, 1e. g., beta-beta'-dicmoro-ciethm ether, 1l

beta-chloro-betaH-bromo-diethyl ether, gammagammaffdib'romodipropyl ether, or the like, in the'presence of water and-a 'suitable alkali, e. g., NaOH; KOH, etc. Applications, Serial Nos. 225,414 and"225,415,'flled concurrently herewith, disclose in detailr the preparation and properties of a largenumberiof' these compounds. The aryl- Oxy-chloro-ethers falling within the scope of the above formula havebeen found to be substantially odorless, colorless, and comparatively innoc-L uous` as regards? their effect' upon human beings andwa'rmbloodedv animals. yParticularly advantageous is y"the fact y that they f do not cause irritationiand dermatitis uponcontact with living tissueand f 30 The method employed. in determining the insecticidalftoxicities of solutions of the above compounds and combinations thereof with pyrethrin and rotenon'` is" substantially that described in Soap, ,8No.. 4, 1'932 known as the Peet-Grady 35 method. Knockdownand mean kmortality figures as shown in the subsequent examples for the most partepresent 'averages of'results obtained `in a series, of runs -forthe yparticular compositions concerned.1 The terms1"p`er cent and percentv Y 40 age. as employed .in the specification `and claims,

with referencefto the compositionjof various spray `materialaf.;refer'Tto .`grams per'V 100 milliliters thereof. *Forpurpose ofcomparison, in the expourvoi i379 :,F. f

invention'v vi1 luvst :raf.fry fthe rouowlng Knock- Mean mor- Percentage toxicant in oil down in 10 tality in minutes 48 hours l 53 36 3 92 60 4. 94 80 Control solution. 100 *53 The test solutions were substantially odorless.

non-irritating, and colorless, and did not decompose or deteriorate on storage and exposure to light and air.

. Example 2 y A 2 per cent solution of beta-(2.4,6-trichlorophenoxy)-beta'chlorodiethyl ether in the pyrethrin-containing control solution was prepared and tested substantially as described in Example 1. This spray material -knocked down A100 per cent in 10 minutes, killed 83 per cent of the ilies in 48 hours, and was non-irritating to the nasal passages of humans. A portion of the above composition was compared with the control solution to determine the resistance of the two materials to decomposition upon exposure to air and light. After one week exposure. the control solution was found to knock down 96 per cent and to kill 36 per cent of the test flies in 48 hours. 'I'he combination o1' the control solution and 2 per cent of the syntheticether compound knocked down 99 per cent of the test insects in 10 minutes and killed 77 per cent in 48 hours after a similar exposure.

Example 3 A Other aryloxy-halo-dialkyl ethers were tested by the Peet-Grady method to determine their efflciency as ily spray toxicants. The data set forth in the following table is representative of that obtained from 3 per cent solutions of such toxibetach1orodiethyl ether, boiling at 166170 C. at 3 millimeters pressure and having the speciflc gravity 1.151 at 20/4 C.; and beta-(2,6- dichloro4tertiarybutyl-phenoxy) -betachloro diethylether. boiling at 179-l80 C. at 4 millimeters pressure and having a specific gravity of 1.229 at 20/4 C. Other compounds which may vsimilarly be employed include beta-(2,4,6-trimethyl phenoxy) -beta chloro diethyl ether.' beta (2-bromo-4-normal-amyl-phenoxy) beta-v bromo-diethyl ether, beta-(2-ehloro-4-tertiarybutyl-phenoxy) -betaf-chloro-diethyl ether, gamma- (2,4.6-trichloro-phenoxy) -gammachiorodi propyl ether, beta- (2-bromo-4-methyl-phenoxy) beta'chloroethylpropyl ether, beta-(2,4,6-trichloro phenoxy) betabromo-dipropyl ether, beta-(2methyl4 tertiarybutyl -chloro-phendichloride, hydrogenated naphthalene, butyl alcohol, etc., may be employed provided only that such solvents be inert with respect tothe toxicants employed, non-injurious to humans, -and capable of dissolving the insecticidal plant products and/or aryloxy-halo-dialkyl ethers in the required amounts.

The phrase non-corrosive organic solvent as employed in the following claims refers to any organic solvent material unreactive with, and capable of dissolving the toxicants hereinbefore de-y scribed. and non-injurious to the skin and gen-v cants. eral health of humans.

kiss fue; own mo Compound in 10 minut in 48 hours `Beta(2ehlorophenoxy)betachlorodiothyl other (boiling point lar-136 C. at 2 mm. 23 Beta-(2,4-diohloro-phenoxy)betachlorodiothyl other (boiling point 148-l49 C. at 1.5 mm. I 63 sa pressure -.0

tric ohenox )beta-chlorodietbyl other (melting int 60 C.) 80 47 ttltdibrolpienoxygbetachloro-diethyl other (boiling po t 19V-mi C. at 6 mm. 9o M pnmre) -ma Be 2- 4chlo heno -bots'chlorodiethyl other (density 1.54 at 25 /25 C.) 74 46 Bett: 44h13:o2,6-dicrggro-phgaaxyybetachloro-diethyl ether (density 1.60 at 25:/25 0.). 45 32 Beta- 2br0m 4,6dichlorophenoxy)beta'chlorodiethyl ether (density 1.58 at 25 [25 0.)... 82 53 Beta- 4bromo2methylpbenoxy)bets'chlorodiethyl ether (density 1.43 at 25 [25 C.)-.... 8s Bez?,-l %4d)ichloro6methylphenoxy)beta'chlorodiethyl other (speelde gravity 1.209 at 42 By substituting other aryloxy-halo-dialkyl ethers for those disclosed in the foregoing examples, insecticidal compositons may be obtained of comparable ei'iiciency in the control of household and related insect pests. Representative of such compounds are beta(4-ehloro-phenoxy)beta' chloro-diethyl ether,` a water-white, mobile liquid boiling at 156-159 C. at 3 millimeters pressure and having a specific gravity of 1.250 at 20/4" C.; beta- (2 chloro-4 -tertiarybutyl phenoxy) tinctly claim as our invention:

1. An insecticidal spray comprising as its principal toxic ingredient an aryloxy-halo-dialkyl ether dissolved in a non-corrosive organic solvent.

2. An insecticidal spray comprising a non-corrosive organic solvent having dissolved therein a product selected from the class consisting of the extracts of pyrethrinand rotenone-bearing plants and as an added toxicant and stabilizer an aryloxy-halo-dialkyl ether.

3. An insecticidal spray comprising a non-corrosive organic solvent having dissolved therein a product selected from the class consisting of the extracts of pyrethrnand rotenone-bearing plants and as an added toxicant and stabilizer an aryloxy-halo-dialkyl ether in amount ranging between 0.5 and 10 grams per 100 milliliters thereof.

4. An insecticidal spray comprising a petroleum distillate having dissolved therein as the principal toxic ingredient a compound having the formula l @-o-R-o-R-x x.. I

wherein each R represents an alkyl residue containing not more than 3 carbon atoms, each X represents halogen, Y represents a member of the group consisting of hydrogen and alkyl radicals containing not more than 6 carbon atoms, n is an integer not greater than 5, and m is an integer not greater than 2.

5. An insecticidal spray comprising a petroleum distillate solution of a product selected from -the class consisting of the extracts of pyrethrinand rotenone-bearing plants, and as an additional toxicant and stabilizer a compound having the formula @-o-clm-o-clnr-x Xl @-o-cim-o-cim-ci wherein X represents halogen, and n is an integer not greater than 5, in amount ranging between 0.5 and l grams per 100 milliliters thereof.

'1. An insecticidal spray comprising a petroleum distillate solution of an insectical product selected from the class consisting of the extracts of pyrethrinand rotenone-bearing plants, and as an additional toxicant and stabilizer therein a beta-(alkyl-halo-phenoxy) beta'chlorodiethyl ether having the formula @-o-cinr-o-cm-ci x.. I

wherein X represents halogen, Y represents an alkyl group containing not more than 6 ycarbon atoms, and n is an integer not greater than 4, in amount ranging between 0.5 and 10 grams per 100 milliliters thereof.

8. An insecticidal spray comprising as its principal toxic ingredient beta-(2,4,6-trichloro-phenoxy)-beta'ch1orodiethyl ether dissolved in a non-corrosive organic solvent.

9. An insecticidal spray comprising a petroleum distillate solution of an insecticidal product selected from the class consisting of the extracts of pyrethrinand rotenone-bearing plants,vand as an additional toxicant and stabilizer beta -(2,4,6 trichloro phenoxy) beta'- chloro-diethyl ether dissolved therein.

10. An insecticidal spray comprising a petroleum distillate solution of an insecticidal product selected from the class consisting of the extracts of pyrethrinand rotenone-bearing plants, and as an additional toxicant and stabilizer beta- (2,4,6trich1orophenoxy) beta' chloro diethyl ether dissolved therein in amount ranging between 0.5 and l0 grams per 100 milliliters thereof.

11. An insecticidal spray comprising a petroleum distillate solution of an extract of a pyrethrin-bearing plant, and as an additional toxicant and stabilizer therein beta-(2,4,6-trichlorophenoxy)beta'chlorodiethyl ether in amount ranging between 0.5 and 10 grams per 100 milliliters thereof.

12. An insecticidal spray comprising a noncorrosive organic solvent having dissolved therein as the principal toxic ingredient a compound having the formula:

wherein each R. represents an alkyl radical containing not more than 3 carbon atoms, each X represents halogen. Y represents. a member of the group consisting of hydrogen and alkyl radicals containing not more than 6 carbon atoms, n is an integer not greater than 5, and m is an integer not greater than 2.

GERALD H. COLEMAN. CLARENCE L. MOYLE. 

